Process for copolymerizing ethylene and higher 1-monoolefins



United States Patent 3,367,922 PROCESS FOR COPOLYMERIZING ETHYLENE ANDHIGHER l-MONODLEFINS Richard J. Sonnenfeld and Ollie G. Buck,Bartlesville,

0kla., assignors to Phillips Petroleum Company, a corporation ofDelaware No Drawing. Filed Sept. 12, 1963, Ser. No. 308,338 7 Claims.(Cl. 2ritl80.78)

This invention relates to a process for the copolymerization of ethyleneand higher l-monoolefins. In another aspect, it relates to a continuousprocess for copolymerizing ethylene, at least one higher l-monoolefin,and a monomer which imparts unsaturation to the resulting polymer. Inanother aspect, it relates to a novel charging procedure for use in thecopolymerization of ethylene and higher l-monoolefins.

Many l-monoolefins, such as ethylene and propylene, can be copolymerizedto form copolymers ranging from lovs molecular weight oils to highmolecular weight solids. Recently, commercial interest has developed inthe preparation of elastomeric copolymers of ethylene and propylene,these copolymers having a high molecular weight and a high degree ofresistance to Weathering, sunlight and ozone.

In carrying out the copolymerization of ethylene and higherl-monoolefins according to the prior art, the usual procedure is tocharge the monomers to the polymerization reactor containing a premixed,two-component, activated coordination catalyst, or to charge thepremixed catalyst or the separate components thereof to the reactorfilled with the monomers. Though the polymerization can be carried outsatisfactorily in this manner, there are certain disadvantages attendantsuch charging procedures. For example, if the catalyst is prepared bypremixing the catalyst components and the resulting premixed catalyst isnot immediately employed, oftentimes a precipitate will form and settle,causing obstruction of lines, nozzles, etc. Also, a premixed catalystoften declines or changes in activity upon aging. Where the catalyst isprepared in situ by separately charging the components to a reactorfilled or subsequently filled with monomers, is often difficult tomaintain a constant desired ratio of catalyst components and a desiredcatalyst level. Such charging procedures, consequently, make itdiflicult to control the reaction conditions and the uniformity of thepolymer product.

Accordingly, an object of this invention is to provide an improvedprocess for copolymerizing ethylene and higher l-monoolefins. Anotherobject is to provide an improved continuous process for copolymerizingsuch monomers and a monomer which imparts unsaturation to the resultingpolymer. Another object is to provide in such a polymerization process anovel charging procedure by which close control can be exercised overthe ratio of catalyst components, catalyst level, catalyst activity,reaction conditions, and uniformity of polymer product. Further objectsand advantages of this invention will become apparent to those skilledin the art from the following description and appended claims.

Briefly, the continuous process of copolymerizing ethylene and at leastone other l-monoolefin, such as propylene, in a solvent with apolymerization coordination catalyst comprising a reducible component,such as vanadium tetrachloride or vanadium oxytrichloride, and areducing component, such as ethylaluminum sesquichloride, is improved byseparately and substantially simultaneously charging to thepolymerization reaction zone, a first stream comprising ethylene,solvent, and one of said catalyst components, and a second streamcomprising said higher 1-monoolefins, solvent, and the other of saidcatalyst components. Where the monomeric material also comprises atermonomer, such as dicyclopentadiene,

3,367,922 Patented Feb. 6, 1968 such termonomer is charged is thatstream containing the reducing catalyst component, which streampreferably contains said higher l-monoolefin.

As an illustration of the charging procedure of this invention, tworeservoir or makeup tanks can be provided, each having supply conduitswith flow control valves and the like and flow measuring means such asrotometers for the stream components. The contents from the two makeuptanks are passed by separate conduits, provided with pumps or rotomctersand flow control valves, to the polymerization reactor, initially filledto the desired level with solvent, where the catalyst is formed orgenerated in situ in the presence of the monomers at the desired ratiosand catalyst levels desired during polymerization. The makeup tanks canbe so sized that they are pumped out or emptied at the same time andthese makeup tanks can be provided with suitable agitators or the likefor blending the stream components. The supply of the stream componentsto the makeup tanks can be varied as desired, for example duringpolymerization, to regulate the concentration of the individual streamcomponents, catalyst ratios, etc. The flow rates of the two streams canbe regulated to maintain the desired monomer ratios in the reactor aswell as that of the catalyst components. The reactor is maintained at aconstant liquid volume by regulating the flow of charge streams and thewithdrawal of the efliuent therefrom, and it can be provided withagitators or the like, cooling coils or a cooling jacket, and the usualappurtenances common to polymerization reactors. The polymerizationefiluent can be passed through a pressure release valve and thence to aflash member for removal of vaporized, unreacted monomers, and theflashed efliuent can thereafter be treated with the usual additives,such as antioxidant, and the polymer recovered from the efliuent, forexample by precipitation with an antisolvent, such as isopropyl alcohol.

Since the catalyst is continuously and freshly generated in situ as itis used in polymerization, there is no need to preliminarily filter anyprecipitate which would otherwise form on standing and there is no needto compensate for any decline or change in catalyst activity due toaging. The improved charging procedure of this invention permits closecontrol over reaction conditions and results in the production ofpolymer product with desired uniform properties.

The l-monoolefins which are copolymerized with ethylene or with ethyleneand termonomers such as dicyclopentadiene, according to this invention,can be represented by the general formula CH CHR, where R is an alkylradical having 1 to 6 carbon atoms. Representative l-monoolefins comingwithin the scope of this general formula and useful in this inventioninclude propylene, l-butene, l-pentene, l-hexene, l-octene,3-methyll-butene, 3-methyl-1-pentene, 3-methyl-1-bexene,4-ethyll-hexene, 4,4-dimethyl-1-pentene, 3,3-dimethyl-l-butene,S-methyl-l-hexene, 4-methyl-l-heptene, S-methyl-l-heptene,4,4-dimethyl-1-hexene, 6-methyl-1-heptene, 3,4,4- trimethyl-l-pentene,and the like, including mixtures of two, three or more thereof.

The termonomers which can be copolymerized with ethylene and any one ofthe above-mentioned l-monoolefins, according to this invention, includeany of those known in the art, particularly those which impart ethylenicunsaturation to the polymer and enable the same to be vulcanized withsulfur. Representative termonomers are dicyclopentadiene(3a,4,7,7a-tetrahydro-4,7-methanoindene), acyclic non-conjugated dienessuch as 1,4-pentadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene,3,3-dimethyl-1,5'-hexadiene, 1,7-octadiene, 1,9-decadiene, 6-methyl-1,5-heptadiene, l1-ethy1-l,ll-triadecadiene, and the like; acetylenessuch as acetylene, vinylacetylene, isopropyl- 3 acetylene, and the like;and norbornenes such as 5-methylene-Z-norbornene, and the like.

The relative percentages of the polymers prepared by the improvedprocess of this invention which are attributable to each of the monomersemployed can vary Widely. Generally, the ethylene and higherl-monoolefin comonomers will each make up from 25 to 75 Weight percentof the polymer, and where a termonomer, such as dicyclopentadiene, isemployed, it will generally make up from 0.5 to 20 weight percent of thepolymer. Of course, the nature of the polymer, that is its molecularweight, inherent viscosity, tensile strength, etc., will be dependentupon the monomeric materials charged and their relative ratios and thereaction conditions, and those skilled in the art of polymerization willbe readily able by means of simple routine tests to determine whatconditions are optimum for any particular polymer product desired.

Any of the polymerization coordination catalysts known in the prior artcan be employed in the polymerization process of this invention, suchcatalysts comprising (1) at least one compound of a reducible polyvalenttransition metal of Groups IVB, VB, VIB, VIIB, VIII of the PeriodicTable (e.g., titanium, vanadium, chromium, manganese, iron, cobalt, andnickel), said reducible compound being a halide, oxyhalide, oracetylacetonate, acetate, and (2) at least one reducing compound of ametal of Groups I, II, IIIA, IVA, and VA of the Periodic Table (e.g.,lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium,calcium, strontium, barium, copper, zinc, cadmium, mercury, aluminum,tin, and antimony), which i preferably above hydrogen in theelectromotive series, said reducing compound being an organometalcompound, a metal hydride, an organometal hydride or an organometalhalogen compound. (The Periodic Table referred to herein and in theclaims is shown on page B2 of the Handbook of Chemistry & Physics, 45thedition, published by Chemical Rubber Publishing Co., Cleveland, Ohio.)Preferably, the metal of the reducible compound is vanadium, titanium orchromium, with vanadium trichloride, vanadium tetrachloride, vanadiumoxytrichloride, vanadium oxydichloride, vanadium acetylacetonate,vanadyl acetylacetonate, titanium tetrachloride, tetrabutyl titanate,tertaisopropyl titanate, chromic chloride, chromium acetylacetonate, andchromyl acetylacetone being examples of preferred reducible componentsof the coordination catalyst. Preferably, the reducing compound has thegeneral formula R MX where R is a saturated aliphatic, saturatedcycloaliphatic, or aromatic hydrocarbon radical having from 1 to 20carbon atoms, M is a metal selected from the group consisting oflithium, sodium, potassium, magnesium, calcium, zinc, mercury, aluminum,and tin, X is a halogen selected from the group consisting of chlorine,bromine, and iodine, n is a number from 1 to 4, m is a number from O to2, and n+m is equal to the valence of metal M. The mole ratio of thereducing compound to the reducible compound in the catalyst system canvary Widely, and generally this ratio will be in the range of 1/1 to20/1. The total catalyst level in the reaction system can also varywidely, and generally will be 0.001 to percent by Weight of the totalmonomers, or as expressed in terms of the amount of reducible compound,the catalyst level can be in the range of 0.25 to 40 millimoles (mmoles)per 100 grams of the total monoolefin charged to the reaction system.

Representative reducible transition metal compounds which can be used inmaking up the coordination catalysts used in preparing the polymers ofthis invention include: titanium tetrachloride, titanium tetrabromide,titanium oxydichloride, tetraisopropyl titanate, titanium trichloride,tetra-n-butyl titanate, tetra-2-ethylbutyl titanate, vanadiumtrichloride, vanadium tetrachloride, vanadium oxytrichloride, vanadiumacetylacetonate, vanadyl acetylacetonate, tetra-n-butyl vanadate,tetraethyl vanadate, trimethyl orthovanadate, vanadium oxydichloride,vanadium dichloride, 2-ethylhexyl vanadate, vanadium dibromide, vanadiumpentoxide, chromyl chloride, chromium acetylacetonate, chromylacetylacetonate, chromium chloride, cobaltous chloride, manganesebromide, cuprous chloride, ferric bromide, molybdenum chloride, nickelchloride, and the like, including mixtures thereof.

Representative reducing compounds which can be commingled with any oneof the above-named transition metal compounds to prepare thecoordination catalyst used in this invention include: ethylaluminumsesquichloride, ethylaluminum sesquiiodide, n-butylaluminumsesquibromide, isopropylaluminum sesquichloride, n-hexylaluminumsesquichloride, n-decylaluminum sesquiiodide, trihexylaluminum,triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride,diisobutylaluminum butoxide, triisobutylaluminum, aluminum hydride,isobutylaluminum dichloride, isobutylaluminum dibutoxide,n-butylaluminum dichloride, n-butyllithium, sodium naphthalene,diisobutylzinc, lithium aluminum tetra-ndecyl, lithium aluminumtetra-n-octyl, amylpotassium, tetraphenyltin, diethyltin diiodide,n-butylmagnesium bromide, diphenylcalcium, di-tert-butylzinc,diethylmercury, and the like, including mixtures thereof.

Representative of the coordination catalysts which can be used in thisinvention are those obtained upon commingling vanadium tetrachloride andethylaluminum sesquichloride, vanadium trichloride and ethylaluminumsesquibromide, vanadium oxytrichloride, and n-butylaluminumsesquibromide, vanadium oxydichloride and isopropylaluminumsesquichloride, vanadium acetylacetonate and n-hexylaluminumsesquichloride, vanadium oxydichloride and diisobutylaluminum butoxide,vanadium oxytrichloride and triisobutylaluminum, vanadium oxytrichlorideand aluminum hydride, vanadium dichloride and triisobutylaluminum,vanadium trichloride and isobutylaluminum dichloride, vanadiumtetrachloride and isobutylaluminum dibutoxide, vanadium tetrachlorideand triisobutylaluminum, vanadium tetrachloride and aluminum hydride,Z-ethylhexyl vanadate and triisobutyl= aluminum, titanyl dichloride andisobutylaluminum dichloride, titanium tetrachloride and isobutylaluminumdichloride, titanium tetrachloride and lithium aluminumdidodecyldichloride, titanium tetrachloride and n-decylaluminumsesquiiodide, titanium tetrachloride and sodium naphthalene,tetraisopropyl titanate and triisobutylaluminum, tetraisopropyl titanateand sodium naphthalene, cobaltous chloride and triisobutylaluminum,cobalt brimide or chloride and triisobutylaluminum, manganese bromideand triisobutylaluminum, manganese bromide and diisobutylzinc, chromiumchloride and triisobutylaluminum, chromium acetylacetonate andn-heptylaluminum sesquichloride, cuprous chloride andtriisobutylaluminum, ferric bromide and triisobutylaluminum, molybdenumchloride and triisobutylaluminum, nickel chloride andtriisobutylaluminum, vanadium oxytrichloride and diethylaluminumchloride, vanadium tetrachloride and ethylaluminum dichloride, vanadiumoxydiacetylacetonate and triethylaluminum, trimethyl orthovanadate andtrihexylaluminum, vanadium tetrachloride and trihexylaluminum, vanadiumoxytrichloride and butyllithium, vanadium triacetylacetonate anddiethylaluminum chloride, titanium tetrachloride and trihexylaluminum,vanadium trichloride and trihexylaluminum, titanium trichloride andtrihexylaluminum, titanium dichloride and trihexylaluminum, vanadiumtrichloride and n-butyllithium, vanadium tetrachloride andamylpotassium, vanadium oxytrichloride and sodium naphthalene, vanadiumoxydichloride and diethylmagnesium, vanadium acetylacetonate andbutylmagnesiurn bromide, vanadyl acetylacetonate and diphenylcalcium,chromic chloride and ditert-butylzinc, chromium acetylacetonate anddiethylmercury, chromyl acetylacetonate and tetraphenyltin, titaniumtetrachloride and diethyltin diiodide, tetra-n-butyl titanate anddiethylmagnesium, and the like.

The polymerization reaction of this invention is carried out in theliquid phase system using a solvent, or a mixture of solvents, in whichthe catalyst and polymer product are soluble. As such, the system can bedescribed as a ample 0.1 to 10 phr, can be used for vulcanization,representative peroxides being bis(alpha, alpha-dimethylbenzyl)peroxide, diisopropyl peroxide, di-tert-butyl peroxide, dibenzoylperoxide, alpha, alphadimethylbenzyl hydropersolution polymerizationsystem. The solvent is charged 5 oxide, tert-butyl perbenzoate, etc.vulcanization accelerato the reactor in each of the two feed streams,and the tors, accelerator activators, reinforcing agents,extendconcentration of the monomeric materials in the feed ers,plasticizers, antioxidants and fillers, like those streams can vary andwill be dependent upon the paragents used in compounding natural andsynthetic ticular polymer product desired. Usually, the feed streamrubber, can also be employed. Fillers and reinforcing Containingethylene Will Contain om 1 t 5 eigh agents such as carbon black, clay,calcium silicate, talc, percent of the ethylene in the solvent, and thefe d St am silica, whiting, and titanium dioxide, and plasticizers suchcontaining the higher l-monoolefin will contain the latter as hth i dfli i il can b d i ill a Concentration of about 1 i0 30 Weight Percentin pounding the polymers of this invention. Such polymers the l n Wherea terrnonomer is used, it l be will have molecular weights in the rangeof about 5000 to present generally in the feed stream in the amount of1,000,000, and can be used in fabricating such rubber about to 10 WeightPercent in the Solvent Solvents goods and plastic products as coatingsfor electrical cables, which can be employed include y of those known inwindow-seals, garden hose, soles and heels, belts, coated the Prior andthese ts will s y be a hydrofabrics, tires films coatings, containers(bottles), i es, carbon or halogenated hydrocarbon, such as propane,fiberseta l butane, hexane, benzene, toluene, Xylene, tetrachloro- Theobjects and advantages of this invention are illusethylene, cyclohexane,mthylcyclohexanes Chlombelltrated in the following examples, but itshould be under- Zene, o-dichlofobenlenq, dlchloromethane, 1,1,2,2-tetfastood that the various materials used in these examples,chlowethfmg, and the The P B l as mentlonfi the conditions of operation,and other details, should not above, will be soluble in the solvent andusually will be construed to unduly limit this invention be present in aconcentration of 1 to 15 we1ght percent.

The polymerization reaction of this invention is carried Example I outin the absence of those materials which have a dele- In his example,ethylene/propylene/dicyclopentadiene terious effect on the catalystactivity, such as oxygen, rubbery terpolymers were prepared by fourcontinuous carbon dioxide, and water. The polymerization conditionspolymerization runs according to this invention. In each can varywidely, but generally the polymerization temrun, a l-liter autoclave wasused as the polymerization reperature will be in the range of 80 to 150C. The actor, and it was charged simultaneously with two separeactionpressure, maintained by an inert atmosphere rate feed streams from twomakeup tanks at rates such such as nitrogen, will be that sufilcient tomaintain the that the completion of addition of materials from bothreaction mixture in the liquid phase and can be up to 500 tanks occurredat the same time. At the beginning of each or ore atmospheres. run, 500ml. of toluene was charged to the: reactor, which Followingpolymerization, the polymer product can be had previously been filledwith nitrogen. After charging conventionally recovered from the efiluentby coagulation this solvent, the reactor was pressured with nitrogen towith a non-solvent such as an alcohol like isopropyl alco- 180 p.s.i.g.Introduction of the composite streams was hol or n-butyl alcohol,acetone, or the polymer can be started at the same time and continueduntil the makeup recovered by stripping the solvent with heat or steam.An tanks were emptied. Throughout each run, 500 ml. of maantioxidant canbe incorporated in the polymer during the terial was maintained in thereactor by regulating the withrecovery procedure, such asphenyl-beta-naphthylamine, drawal of efiluent therefrom. In each run,the reaction mixdi-tert-butylhydroquinone, triphenylphosphite,heptylated ture was allowed to remain in the reactor 5 minutes afterdiphenylamine, 2,2-methylene-bis(4-methyl-6-tert-butylpumping of thestreams to the reactor was stopped, and phenol), and2,2,4-trimethyl-6-phenyl-1,2-dihydroquinothe polymerization time for arun is that time the reline. action mixture remained in the reactor.Following polym- Vulcanization or curing of the polymers prepared byerization, the reactor efiluent was flashed to remove unrethis inventioncan be carried out with conventional vulacted ethylene and propylene.Two weight percent of 2,2- canization procedures. Where sulfur isemployed in the vnlmethylene bis(4-methyl-G-tert-butylphenol)antioxidant canization of the polymers, the amount of sulfur used willwas added to the effluent, the rubbery polymer was coagugenerally beabout 0.1 to 5 parts by weight per parts lated with isopropyl alcohol,separated and dried, and the of polymer (phr) and generally about 0.5 to3 phr. The properties of the polymer products were determined. Thevulcanization can be effected, for example, at temperatures compositionof the charge streams, reaction conditions, of 250 to 400 F. for 5 tominutes. Peroxides, for exand polymer properties are set forth in TableI.

TABLE I Runs Stream 1 Stream 2 Stream 1 Stream 2 Stream 1 Stream 2Stream 1 Stream 2 Charge stream components:

Tol

0 0 Trace 61. 5 22 114 7 The polymer products from runs 2, 3 and 4 werecompounded and cured 30 minutes at 320 F. The compounding recipeemployed in all the runs is set forth in Table II.

TABLE II Parts by wt. Polymer blend 100 High abrasion furnace black 50Zinc oxide 5 Stearic acid 1 Circosol ZXH" 30 Sulfur 1.5 Captax 0.5 Monex1.5

Petroleum hydrocarbon softener, containing hydrocarbons of highmolecular weight, in the form of a heavy, viscous, transparent, palegreen, odorless liquid of low volatility; specific gravity, 0.940Saybolt Universal viscosity at 100 I about 2000 seconds.

b 2-mercaptobenzothlazole.

, c 'letramethylthiuram monosulfide.

The Mooney viscosity of the compounded polymers and the properties ofthe cured polymer products are set forth in Table III.

Example 11 In this example, an ethylene/propylene/vinylacetyleneterpolymer was prepared according to this invention, using the procedureof Example I. Stream compositions, reaction conditions, and theproperties of the recovered terpolymer are set forth in Table IV.

TABLE IV Stream 1 Stream 2 Charge stream components:

Toluene, ml 1, 600 1, 600 Ethylene, gm 80 Propylene, gm 0 200Vinylacetylene, gm 0 8.3 Vanadium tetrachloride, mmoles. 4 0Ethylaluminum sesquichloride, mmol 0 10 Charge stream pump rate, nil/min37 42 VCh/EASO mole ratio 2.5/1 Flow rate through reactor, vol. totalfeed/liq.

vol. reactor/hr 9. 4 Polymerization temp, F 80 Polymerization time, min52 Conversion (based on ethylene and propylene),

wt. percent 20. 8 Polymer properties:

Wt. percent of propylene units in polymer.. 33 Total unsaturation,mmoles. ICl/gm. polymer 0. 33 Inherent viscosity 1. 04

TAB LE V Cure time, min.

300% Modulus, p.s.i 1,350 1, 580 Tensile, p.s.i 2, 505 2, 850Elongation, percent- 535 50-5 Resilience, percent..- 62. 5 61. 8 Shore Ahardness 86. 5 88 In the foregoing examples, the procedure used todetermine total unsaturation by iodine chloride titration was asfollows: A 0.5-gram sample of polymer was dissolved in a /25 volumemixture of carbon disulfide and chloroform, a chloroform solution ofiodine chloride of known concentration (approximately 0.090.10 molar)was added, the mixture was placed in a 25 C. bath for one hour to allowtime for reaction, and the excess of iodine chloride was titrated with0.05 N sodium thiosulfate. The millimoles of iodine chloride thatreacted with one gram of sample was then calculated. A blank was runusing only solvent and iodine chloride and appropriate correction wasmade when calculating unsaturation.

In the examples, an infrared procedure was used to determine the wt.percent propylene. A carbon tetrachloride solution of the polymercontaining one gram of polymer per 100 milliliter solvent was used. Thesolution Was placed in a ISOO-micron cell and scanned for a peak at the7.25 micron band using a commercial infrared spectro photometer. Thenumber of methyl groups (N) was obtained from the formula:

-WLZ5)(1,000) T (0) (o 1 The specifiic extinction coefiicient (e=28,700)was determined using three samples of an ethylene/ propylene copolymerof known propylene content as a reference material. The value wasobtained by solving the equation N) II d Density of polymer solution ingm./ cc. (assumed to t=Thickness of absorbing layer of polymer incentimeters; N :Number of methyl branches in control polymer.

The percent propylene was calculated as follows:

333 III In the Formula III, 333 is the number of methyl branches per1,000 methylene groups.

The inherent viscosities referred to in the examples were determined byplacing one tenth gram of polymer in a wire cage made from mesh screenand placing the wire cage in ml. of toluene contained in a wide-mouth4-ounce bottle. After standing at room temperature (approximately 25 C.)for 24 hours, the cage was removed and the solution was filtered througha sulfur absorption tube of grade C porosity to remove any solidparticles present. The resulting solution was run through a Mediatypeviscometer supported in a 25 C. bath. The viscometer was previouslycalibrated with toluene. The relative viscosity is the ratio of theviscosity of the polymer solution to that of toluene. The inherentviscosity is calculated by dividing the natural logarithm of therelative viscosity by the weight of the soluble portion of the originalsample.

The amount of toluene insolubles referred to in the examples is thatamount of material not dissolved after 0.2 gram sample of the polymerremains in contact with 100 milliliters of toluene at room temperaturefor 24 hours. The value should be below 50 weight percent for a rubberypolymer. Ordinarily, it is preferred to have the value below 25 weightpercent, but for some uses (mechanical goods, mats, shoe soles, etc.) itcan be higher. For uses where high resilience and low heat build-up areimportant, it is desirable to have the toluene insolubles low.

Various modifications and alterations of this invention Percent willbecome apparent without departing from the scope and spirit of thisinvention and it should be understood that this invention is not to belimited unduly to that set forth herein for illustrative purposes.

We claim:

1. In a continuous process for solution polymerizing ethylene and atleast one higher l-monoolefin With a twocomponent soluble polymerizationcoordination catalyst comprising at least one compound of a reduciblepolyvalent transition metal of Groups IVB, VB, VIB, VIIB and VIII, andat least one reducing compound of a metal of Group I, II IIIA, IVA, andV, the improvement comprising separately and simultaneously charging toa polymerization reaction zone a first feed stream comprising saidethylene, solvent, and one of said catalyst components and the secondfeed stream comprising said higher l-monoolefin, solvent, and the otherof said catalyst components and Withdrawing efiluent therefrom at a ratesuflicient to maintain a constant liquid volume in said reaction zone.

2. In a continuous process for solution polymerizing ethylene and atleast one higher l-monoolefin of the general formula CH =CHR, where R isan alkyl radical having 1 to 6 carbon atoms, with a two-componentsoluble polymerization coordination catalyst comprising at least onecompound of a reducible polyvalent transition metal of Groups IVB, VB,VIB, VIIB and VIII, and at least one reducing compound of a metal ofGroup I, II, IIA, IVA and V, the improvement comprising separately andsimultaneously charging to a polymerization reaction zone a first feedstream comprising said ethylene, solvent, and one of said catalystcomponents and the second feed stream comprising said higherl-monoolefin, solvent, and the other of said catalyst components andwithdrawing effluent therefrom at a rate sufiicient to maintain aconstant liquid volume in said reaction zone.

3. In a continuous process for solution polymerizing ethylene, at leastone higher l-rnonoolefin of the general formula CH CHR, Where R is analkyl radical of 1 to 6 carbon atoms, and a termonomer Which impartsunsaturation to the resulting polymer with a two-component solublecoordination catalyst comprising at least one compound of a reduciblepolyvalent transition metal of Groups IVB, VB, VIB, VIIB and VIII, andat least one reducing compound of a metal of Group I, II, IIIA, IVA, andV, the improvement comprising separately and substantiallysimultaneously charging to a polymerization reaction zone a first feedstream comprising said ethylene, solvent, and one of said catalystcomponents and a second feed stream comprising said higher l-Inonoolefinsolvent and the other of said catalyst components, said termonomer beingcharged to said polymerization zone in that said feed stream containingsaid reducing catalyst component and Withdrawing effiuent therefrom at arate sufficient to maintain a constant liquid volume in said reactionzone.

4. The process according to claim 3 wherein said termonomer and saidreducing catalyst component are present in said second feed stream.

5. The process according to claim 4, wherein said termonomer isdicyclopentadiene.

6. In a continuous process for solution polymerizing ethylene, propyleneand dicyclopentadiene in toluene with a polymerization coordinationcatalyst comprising ethylaluminum sesquichloride and vanadiumtetrachloride, the improvement comprising separately and substantiallysimultaneously charging to a polymerization reaction zone a first feedstream comprising said ethylene toluene. and vanadium tetrachloride anda second feed stream comprising said propylene, dicyclopentadiene,toluene and ethylaluminum sesquichloride and Withdrawing eflluenttherefrom at a rate sufficient to maintain a constant liquid volume insaid reaction zone.

7. In a continuous process for solution polymerizing ethylene, propyleneand vinylacetylene in toluene With a polymerization coordinationcatalyst comprising ethylaluminum sesquichloride and vanadiumtetrachloride, the improvement comprising separately and substantiallysimultaneously charging to a polymerization reaction zone a first feedstream comprising said ethylene, toluene, and vanadium tetrachloride anda second feed stream comprising said propylene, vinylacetylene, tolueneand ethylaluminum sesquichloride and withdrawing efiiuent therefrom at arate sufficient to maintain a constant liquid volume in said reactionzone.

References Cited UNITED STATES PATENTS 3,291,784 12/1966 Bebbington eta1. 260-94.9 3,166,538 1/1965 Olson et al. -260-88.2 3,211,709 10/1965Adamek et a1. 26080.5

FOREIGN PATENTS 538,782 6/1955 Belgium.

856,736 12/ 1960 Great Britain.

857,183 12/1960 Great Britain.

857,938 1/ 1961 Great Britain.

JOSEPH L. SCI-IOFER, Primary Examiner. M. B. KURTZMAN, W. HOOVER,Assistant Examiners.

1. IN A CONTINUOUS PROCESS FOR SOLUTION POLYMERIZING ETHYLENE AND ATLEAST ONE HIGHER 1-MONOOLEFINE WITH A TWOCOMPONENT SOLUBLEPOLYMERIZATION COORDINATION CATALYST COMPRISING AT LEAST ONE COMPOUND OFA REDUCIBLE POLYVALENT TRANSITION METAL OF GROUPS IVB, VB, VIB, VIIB ANDGROUP I, II, IIIA, IVA, AND V, THE IMPROVEMENT COMPRISING SEPARATELY ANDSIMULTANEOUSLY CHARGING TO A POLYMERIZATION REACTION ZONE A FIRST FEEDSTREAM COMPRISING SAID ETHYLENE, SOLVENT, AND ONE OF SAID CATALYSTCOMPONENTS AND THE SECOND FEED STREAM COMPRISING SAID HIGHER1-MONOOLEFIN, SOLVENT, AND THE OTHER OF SAID CATALYST COMPONENTS ANDWITHDRAWING EFFLUENT THEREFROM AT A RATE SUFFICIENT TO MAINTAIN ACONSTANT LIQUID VOLUME IN SAID REACTION ZONE.